Azo dyestuffs and process of making them



Patented Feb. 11, 1930 UNITED STATES PATENT OFFICE HANS HEYNA, OF HOCHST-ON-THE-MAIN, WERNER KIRS'I, OF FRANKFORT-ON-THE- MAIN, AND HERBERT KRACKEB. AND KARL 1V1OLDA."EJQ'KIE OF HOCHST-ON-THE-MAIN,

GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, IN (3., OF NEW YORK, N. Y., A

CORPORATION OF DELAWARE AZO DYESTUFFS AND PROCESS OF MAKING THEM No Drawing. Application filed March 13, 1928, Serial No. 261,408, and in' Germany March 21, 1927.

Our present invention relates to azo dyestuffs and process of making them.

We have found that azo-dyestufl's can be obtained by coupling a diazo-compound of a dihalogen substitution product of metatoluidine with a compound capable of beingtaken up by vegetable fiber and capable of being coupled, for instance, an arylamide of .2.3-hydroxynaphthoic acid.

The dyestufis may be made in substance or in presence of a suitable substratum, or they may be produced directly on the fiber. The dyeings obtainable with the dyestuffs are distinguished by their fastness to kier-boiling and to chlorine, and in particular by their excellent fastness to light.

The following examples illustrate the in-.

1 liter Developing bath 3.52 grams of 1-amino-2.4-dichloro-3-methylbenzene are made into a paste with a small quantity of water and 5.2 cc. of hydrochloric acid of 22B.;

to this paste there are added v by portions ice and 1.44 grams, of sodium nitrite in the form of a solution. \Vhen the diazotizationis complete, the mass is neutralized by means of grams of sodium acetate and the whole is made up with water to .1 liter 50'grams of well boiled cotton yarn are treated with the grounding solution for half an hour, well freed from water by wringing out and centrifuging and dyedin the diazosolution for 1 minute. has been thoroughly. rinsed, the dyeing is soaped at boiling temperature and rinsed. The dyeing produced is Vivid scarlet and is fast to kier-boiling, chlorine and light.

The dyestulf has probably the following formula (2) Grounding liquor 2.5 grams of 2.3-hydroxynaphthoic acid-2- naphthalide 5 cc. of sodium Turkey red oil of 50 per cent strength, and

7.5 cc. of caustic soda solution of 34 B. are dissolved with the aid of hot water. After cooling there are added 2.5 cc. of formaldehyde and the whole is made up with water to 1 liter Developing bath 3.52grams of 1-amino-4.6-dichloro-3-methylbenzene are made into paste with I of hydrochloric acid of 22 B.

anda small quantity of water and to this paste are gradually added a solution of of sodium nitrite together with some ice. When diazotization is complete, the whole is neutralized by means of grams of sodium acetate and made up with water to 1.44 grams 1 liter The material is dyed in scribed in Example (1) the dyeing is vivid red fast to kier-boiling and to light.

After the materialv the manner de- The dyestufi formula:

(3) Gran/riding liquor 4.5 grams of 2.3-hydroxynapht'hoic acid- 2.5-dimethoxy-1-anilide,

.of sodium Turkey red oil of per cent strength, and

of caustic soda solution of 34 B. are dissolved with aid of boiling water and after cool- .ing there are added of formaldehyde of 30 per cen strength and the whole is made up withwater to 1 liter Developing both 3.52 grams of 1-amino-4.6-dichloro-3-methylbenzene are made into a paste with 5.2 cc. of hydrochloric acid of 22 B.

and a small quantity of water and to the paste'so obtained are gradually added a solution of a 1.44 grams of sodium nitrite together with some ice. When diazotization is complete, the mass is neutralized with 4 grams of sodium acetate and made up with water to N=N OOH 1 H co-NHQ (4). Grounding liquor 4 grams of 2.3-hydroxynaphthoic acid-5- chloro-2-anisidide,

has probably the following 1 liter Developing bath 7 3.52 grams of 1-amino-4.5 -dichloro-3-methylbenzene are made into a paste with 5.2 cc. of hydrochloric acid (rt-22 cc. and a small quantity of water and to this paste are gradually added a small quantity of a5 ice and a solution of I 1.44 grams of sodium nitrite. When diazotization is complete, the mass is neutralized with 4 grams of sodium acetate and made up to Y 1 liter The material is dyed in'the manner described in Example (1), whereby there is ob tained a vivid yellowish scarlet fast to kierboiling, chlorine and light.

The dyestufi has probably the following formula:

v i 01 N=N H co-NH-O-o (5) Grounding liquor 4.5 grams of 2.3-hydroxynaphthoic acid- 2.5-dimethoxy-1-anilide,

9 cc. of sodium Turkey red oil of 50 per cent strength, and 1125 cc. of caust c soda solution of 34 B6. are dissolved with the aid of boiling water, and after cooling there are added 4.5 cc. of formaldehyde of 30 per cent strength and the whole is made up to 1 liter Developing bath 3.52 grams of hydrochloric acid of 22 B. and a small quantity of Water and to this paste there are added a small quantity of ice and asolution of 1.44 grams of sodium nitrite. When diazotization is complete there are added about 4 grams of sodium acetate until the solutowards Congo paper and the whole is then made up to 1 liter The dyeing obtained by dyeing material in the manner described in Example (1) is a brownish-orange fast to light and of moderately good fastness to kier-boiling.

The dyestufi' has probably the following formula:

OCH: (6) Grounding lignor 4.5 grams of 2.3-hydroxynaphthoic acid-5- chloro 2 toluidide are dissolved in Water at boiling temperature together with of sodium Turkey red oil of 50 per cent strength and of caustic soda solution of 34 B.; the whole is cooled'and there are then added of formaldehyde. The solution is made up to e 1 liter Developing bath 5.3 grams of 1-amino4.5-dibromo-3-methylbenzene are made into a paste with of hydrochloric acid of 22 B. and a small quantity o'fwater I 5.2 cc.

and to this paste are added some ice and a solution of v 1.44 grams of sodium nitrite. After diazotization is complete sodium 55 acetate is added until the mass shows a neutral reaction towards Congo paper and the whole is then made up to 1 liter The dyeing obtained by dyeing rial in the manner described in Example (1) is a vivid scarlet fast to kier-boiling and of 05 good fastness to light.

tion shows a neutral reaction CH: I 00L 4 OCH Cl N=N oo-nnthe mate- I The dyestuif has probably the following formula:

strength. The solution is then made up to 1 liter Developing bath a 5.3 grams of 1-amino-4.6-dibromo-3-methylbenzene are made into a paste with of hydrochloric acid of 22 B. and a small quantity of water and to this paste there are added a small quantitymf ice and a solution of i 1.44 grams of sodium nitrite. lVhen diazotization is complete there are added about 7 sodium acetate until the mass shows a neutral reaction towards Congo paper. The whole is then made up to 4 grams of 1 liter By dyeing the material in the manner described in Example (1), there'is obtained a bluish-red of good fastness to light and moderately good fastness to kier-boiling.

The dyestufi' has probably the following formula:

1, As new products, the azo dyestuffs of the I following general formula of sodium Turkey red oil of 50 X 63 !70Naryl 7 wherein Hlg stands for a halogen atom, one X likewise for a halogen atom, the other X stand for hydrogen atoms and aryl stands for an aryl group free from SU OH or COOH groups, being yellow to brown powders and yielding when produced on the fiber yellow to brown and yellow to bluish-red dyeings of excellent fastness properties.

3. As new products, the azo dyestuffs of the following formula:

. x C I IflN=N8 2': (a do-N-u 1 v i t whereinone X stands for a halogen atom, the other X stand for hydrogen atoms and the ar 1 stands for an aryl roup free from 30,0 or COOH groups, eing yellow to brown powders and yielding when produced on the fiber yellow to brown and yellow to bhiish-red'dyeings of excellent fastness properties." 4 As new products,-the azo dyestuffs of thefollowing formula m. OH;

O-N-aryl wherein the axial stands for an aryl roup free from S0, H or COOH groups, eing yellow to brown powders and yielding when produced on the fiber yellow to brown and yellow to bluish-red dyeings of excellent fastness properties.

being a red powder and yielding when produced on the fiber a vivid red dyeing of good fast-ness to kier-boiling and to light.

In testimony whereof, we aflix our signatures.

HANS IIEYNA.

WERNER KIRST. HERBERT KRACKER. KARL MOLDAENKE.

5. As a new product, the azo dyestufi' of i the following formula: 

